EP0073945B1 - Verfahren zur Gewinnung reiner Aromaten - Google Patents

Verfahren zur Gewinnung reiner Aromaten Download PDF

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Publication number
EP0073945B1
EP0073945B1 EP82107282A EP82107282A EP0073945B1 EP 0073945 B1 EP0073945 B1 EP 0073945B1 EP 82107282 A EP82107282 A EP 82107282A EP 82107282 A EP82107282 A EP 82107282A EP 0073945 B1 EP0073945 B1 EP 0073945B1
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EP
European Patent Office
Prior art keywords
distillation
extraction stage
aromatics
column
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP82107282A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0073945A1 (de
Inventor
Gerhard Dr. Dipl.-Chem. Preusser
Martin Schulze
Gerd Dipl.-Ing. Emmrich
Hans-Christoph Schneider
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Krupp Koppers GmbH
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Krupp Koppers GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Krupp Koppers GmbH filed Critical Krupp Koppers GmbH
Priority to AT82107282T priority Critical patent/ATE13175T1/de
Publication of EP0073945A1 publication Critical patent/EP0073945A1/de
Application granted granted Critical
Publication of EP0073945B1 publication Critical patent/EP0073945B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/08—Azeotropic or extractive distillation

Definitions

  • the invention relates to a process for obtaining pure aromatics from hydrocarbon mixtures which, in addition to these aromatics, contain an arbitrarily high content of non-aromatics, by extractive distillation with N-substituted morpholines as a selective solvent, a predistillation being associated with the extraction stage.
  • the pre-distillation is used to separate certain constituents from the feed before entering the extraction stage. If the feed product contains several aromatics, e.g. B. contains benzene, toluene and xylenes, the extract freed from the solvent must be further broken down into the constituents mentioned in a distillation downstream of the extraction stage (redistillation).
  • aromatics e.g. B. contains benzene, toluene and xylenes
  • the method used to achieve this object is characterized according to the invention. that the pre-distillation is carried out at elevated pressure up to 20 bar and at temperatures up to 30 ° C, the pressure being adjusted in each case so that the pre-distillation can be operated at a higher temperature than the extraction stage and the heat content of the vapors obtained for heating the column is used in the extraction stage operated at low temperature.
  • the process according to the invention thus provides a heat bond between the extraction stage operated as an extractive distillation and the pre-distillation in such a way that the pre-distillation is operated at elevated temperatures using elevated pressures which utilize the heat content of the vapors produced to heat the columns in the extraction stage allowed.
  • energy savings can be achieved in relation to the overall process that can amount to more than 40%.
  • the process according to the invention is generally carried out in such a way that the pre-distillation is carried out under elevated pressure up to 20 bar, while the extraction stage is carried out under normal pressure or under moderately elevated pressure up to a maximum of 3 bar.
  • the extraction stage single or multi-stage extractive distillation can be used.
  • a combination of extractive distillation and liquid-liquid extraction can also be used.
  • the vapors generated in the pre-distillation can not only be used to heat the extractive distillation columns and the associated stripping columns. Some of these vapors can also be used in indirect heat exchange to preheat the feed product.
  • the reflux ratio to be maintained in the pre-distillation is not determined solely by the separation task to be mastered, as is otherwise customary.
  • the reflux ratio and the number of trays in the pre-distillation column are rather chosen so that the amount of steam obtained at the top of the column is sufficient for the column heating in the extraction stage and the preheating of the feed product which may be necessary.
  • Suitable starting materials for the process according to the invention are preferably coke oven benzene pressure refinate, hydrogenated pyrolysis gasoline, reformate gasoline and other hydrocarbon mixtures containing benzene, toluene and xylenes.
  • the vapors obtained can possibly have a higher content of certain non-aromatics, such as. B. methylcydohexane.
  • non-aromatics such as. B. methylcydohexane.
  • these vapors represent the feed for the downstream extraction stage after their condensation, problems could arise from this because these non-aromatics are very difficult to separate from the aromatics when using certain solvents in the extraction stage.
  • these problems are avoided in the process according to the invention in that it is linked to the use of N-substituted morpholines as a selective solvent.
  • N-formylmorpholine in particular has proven to be a suitable solvent.
  • the solvents mentioned above can be used with or without the addition of water. If water is added to the solvent, this is normally between 0 and 8% by weight for the extractive distillation.
  • the flow diagram shown only shows the devices that are absolutely necessary for the process explanation, while other auxiliary devices, such as valves and pumps, are not shown.
  • the aromatics-containing hydrocarbon mixture serving as the feed product is introduced via line 5 and heat exchangers 3 and 4 into the central part of the pre-distillation column 1, which is provided with trays and operated under increased pressure.
  • the bottom circulation boiler 2 At the foot of this column is the bottom circulation boiler 2, the tube system of which can be heated with high pressure steam or via an oven (not shown).
  • the vaporous top product of the pre-distillation is withdrawn via line 6 at the top of the pre-distillation column 1.
  • the steam flow in line 6 is divided into two partial flows.
  • the smaller partial flow of the overhead product vapors also passes from line 6 via line 13 into the tube system of the indirect heat exchanger 3, in which the sensible heat of the vapors is used to preheat the feed product.
  • the condensates accumulating behind the heat exchanger 3 and the sump circulation boilers 8 and 11 reach the collecting line 14, which leads to the collecting container 16, as shown in the flow diagram.
  • the condensed top product from the pre-distillation column 1 is collected in this. The same is withdrawn from the collecting container 16 via the line 17.
  • the line 17 leads to the top of the pre-distillation column 1, so that a small part of the top product can be fed back to the pre-distillation column 1 as reflux.
  • the majority of the same is introduced via line 18 as a feed product into the central part of the bottomed extractive distillation column 12.
  • the extraction stage i.e. H. in the extractive distillation column 12 and the associated stripping column 9 work is carried out at a pressure which is considerably below the operating pressure of the pre-distillation column 1. Otherwise, the extraction stage is operated according to the known principles of extraction distillation. This means that the non-aromatics of the feed product are withdrawn via the line 19 overhead from the extractive distillation column 12, while the aromatics-containing extract is removed from the bottom of this column via line 20 and introduced into the stripping column 9. In this, the aromatics obtained as an extract are separated by distillation from the selective solvent also contained in the extract.
  • the bottom product from the pre-distillation column 1 is withdrawn through line 24 and passes via the heat exchanger 4 into the collecting container 25, from which it is fed via line 15 for its further use.
  • the heat contained in the bottom product is transferred to the feed product in line 5 in indirect heat exchange.
  • This example relates to the production of pure benzene from a pressure-refined coke oven crude benzene, the feed product being first subjected to a pre-distillation according to the flow diagram and the overhead product obtained being further treated in an extractive distillation with N-formylmorpholine as a selective solvent.
  • the input product has the following composition:
  • Part A of the experiment uses the state of the art. This means that the feed product is subjected to a pre-distillation at normal pressure (pressure at the top of the column at most 1.1 bar), the overhead product being introduced into the downstream extractive distillation column, which is operated at a pressure of 2 bar. In this case, a thermal bond in the sense of the present invention does not take place between the pre-distillation and the extraction stage.
  • the pure benzene obtained as the top product of the stripping column contains 100 ppm of toluene and 350 ppm of non-aromatics as impurities. The benzene yield is 99.8%.
  • the total heat requirement of the process is:
  • the heat requirement of pre-distillation at elevated pressure is lower despite a somewhat higher reflux ratio because the heat of vaporization is approx. 30% lower at the pressure used.
  • the overhead product steam temperature of 209 ° C is completely sufficient. In fact, only 80-90% of the amount of overhead vapor is normally required to heat the extraction stage so that the rest can be used to preheat the feed.
  • the total heat requirement for part B can therefore only be estimated at 1270 kJ / kg benzene.
  • This example relates to the production of pure benzene from a fully hydrogenated pyrolysis gasoline.
  • the input product has the following composition:
  • test procedure corresponds to the procedure chosen in Example 1.
  • the pure benzene obtained contains 100 ppm toluene and 400 ppm non-aromatics as impurities.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
EP82107282A 1981-09-05 1982-08-11 Verfahren zur Gewinnung reiner Aromaten Expired EP0073945B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82107282T ATE13175T1 (de) 1981-09-05 1982-08-11 Verfahren zur gewinnung reiner aromaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813135319 DE3135319A1 (de) 1981-09-05 1981-09-05 "verfahren zur gewinnung reiner aromaten"
DE3135319 1981-09-05

Publications (2)

Publication Number Publication Date
EP0073945A1 EP0073945A1 (de) 1983-03-16
EP0073945B1 true EP0073945B1 (de) 1985-05-08

Family

ID=6141028

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82107282A Expired EP0073945B1 (de) 1981-09-05 1982-08-11 Verfahren zur Gewinnung reiner Aromaten

Country Status (12)

Country Link
US (1) US4586986A (xx)
EP (1) EP0073945B1 (xx)
JP (1) JPS5855435A (xx)
AT (1) ATE13175T1 (xx)
AU (1) AU563585B2 (xx)
CA (1) CA1184145A (xx)
DE (2) DE3135319A1 (xx)
ES (1) ES514924A0 (xx)
IN (1) IN158839B (xx)
MX (1) MX161980A (xx)
SU (1) SU1205755A3 (xx)
UA (1) UA6080A1 (xx)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5124004A (en) * 1983-08-22 1992-06-23 Trustees Of Dartmouth College Distillation process for ethanol
US4961826A (en) * 1986-02-13 1990-10-09 Trustees Of Dartmouth College Distillation process for ethanol
DE3612384A1 (de) * 1986-04-12 1987-10-15 Krupp Koppers Gmbh Verfahren zur herstellung eines zur verwendung als blendingkomponente fuer vergaserkraftstoffe geeigneten aromatenkonzentrates
US4824527A (en) * 1986-06-10 1989-04-25 Erickson Donald C Nested enrichment cascade distillation of unequal mixtures
DE3805383A1 (de) * 1988-02-20 1989-08-31 Krupp Koppers Gmbh Verfahren zur herstellung eines zur verwendung als blendingkomponente fuer vergaserkraftstoffe geeigneten aromatenkonzentrates
DE3942950A1 (de) * 1989-12-23 1991-06-27 Krupp Koppers Gmbh Verfahren zur gleichzeitigen gewinnung von reinem benzol und reinem tuluol
US5225072A (en) * 1990-08-03 1993-07-06 Uop Processes for the separation of aromatic hydrocarbons from a hydrocarbon mixture
DE4037060A1 (de) * 1990-11-22 1992-05-27 Krupp Koppers Gmbh Verfahren zur aufarbeitung des sumpfproduktes von extraktivdestillationsprozessen zur gewinnung reiner aromaten
DE4101848A1 (de) * 1991-01-23 1992-07-30 Krupp Koppers Gmbh Verfahren zur abtrennung von aromaten aus kohlenwasserstoffgemischen beliebigen aromatengehaltes
US5310480A (en) * 1991-10-31 1994-05-10 Uop Processes for the separation of aromatic hydrocarbons from a hydrocarbon mixture
MX9401253A (es) * 1993-02-17 1994-08-31 Exxon Chemical Patents Inc Produccion de una corriente de benceno concentradomediante separacion por extraccion.
DE4437702C1 (de) * 1994-10-21 1995-11-23 Krupp Koppers Gmbh Verfahren zur Gewinnung von reinem Benzol und reinem Toluol
US5573645A (en) * 1995-06-29 1996-11-12 Mobil Oil Corporation Process and apparatus for the separation of aromatic hydrocarbons
DE19623291A1 (de) * 1996-06-11 1997-12-18 Basf Ag Verfahren zur Herstellung von schwefelarmen aliphatischen Verbindungen
AUPO775697A0 (en) * 1997-07-07 1997-07-31 Inland Oil Refiners (Qld) Pty Ltd Method and apparatus for fractional distillation
AU725868B2 (en) * 1997-07-07 2000-10-26 Ior Energy Pty Ltd Method and apparatus for fractional distillation
US7687674B2 (en) 2006-12-28 2010-03-30 Uop Llc Low temperature process for recovering and producing para-xylene and heat exchange network therefore
US9005405B2 (en) * 2012-03-01 2015-04-14 Cpc Corporation, Taiwan Extractive distillation process for benzene recovery
KR101550150B1 (ko) * 2013-08-01 2015-09-03 주식회사 엘지화학 정제 장치 및 이를 이용한 정제 방법
KR102308606B1 (ko) * 2017-08-25 2021-10-06 주식회사 엘지화학 비점 차이가 작은 혼합물의 분리 정제 방법

Family Cites Families (15)

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DE347828C (de) * 1920-02-01 1922-01-25 Konrad Kubierschky Dr Verfahren zum Distillieren von Fettsaeuren
US2168570A (en) * 1935-05-31 1939-08-08 Lummus Co Solvent recovery
US2276089A (en) * 1937-06-26 1942-03-10 Union Oil Co Recovery of solvents from oils
US2400370A (en) * 1943-11-11 1946-05-14 Acme Coppersmithing & Machine Process and apparatus for producing in the pure state, butyl alcohol, acetone, and ethyl alcohol from watery solutions
US3639497A (en) * 1968-08-22 1972-02-01 Badger Co Extraction and multi-stage fractional distillation with indirect heat exchange of liquid and vapor process and system for recovering aromatic products
DE2040025A1 (de) * 1970-08-12 1972-02-24 Koppers Gmbh Heinrich Verfahren zur Gewinnung von hochreinen Aromaten aus Kohlenwasserstoffgemischen,die neben diesen Aromaten einen beliebig hohen Gehalt an Nichtaromaten aufweisen
US4081355A (en) * 1970-08-12 1978-03-28 Krupp-Koppers Gmbh Process for recovering highly pure aromatics from a mixture of aromatics and non-aromatics
JPS521471B2 (xx) * 1972-04-20 1977-01-14
JPS5416414A (en) * 1977-07-08 1979-02-07 Kyowa Hakko Kogyo Co Ltd Preparation of absolute ethanol
DE2745672A1 (de) * 1977-10-11 1979-04-12 Metallgesellschaft Ag Verfahren zur gewinnung von aromatenfreiem n-hexan
JPS5490122A (en) * 1977-12-27 1979-07-17 Chiyoda Chem Eng & Constr Co Ltd Distillation of multi-component hydrocarbon composition
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DE3038497C2 (de) * 1980-10-11 1983-11-10 Bayer Ag, 5090 Leverkusen Verfahren und Vorrichtung zur Trennung von ein Azeotrop bildenden Gemischen
JP3060651B2 (ja) * 1991-10-18 2000-07-10 ダイキン工業株式会社 登録分子付加方法

Also Published As

Publication number Publication date
JPH0251407B2 (xx) 1990-11-07
SU1205755A3 (ru) 1986-01-15
AU8797982A (en) 1983-03-17
MX161980A (es) 1991-03-14
DE3135319A1 (de) 1983-03-24
ES8304902A1 (es) 1983-04-16
CA1184145A (en) 1985-03-19
ES514924A0 (es) 1983-04-16
IN158839B (xx) 1987-01-31
AU563585B2 (en) 1987-07-16
JPS5855435A (ja) 1983-04-01
DE3263677D1 (en) 1985-06-13
UA6080A1 (uk) 1994-12-29
ATE13175T1 (de) 1985-05-15
EP0073945A1 (de) 1983-03-16
US4586986A (en) 1986-05-06

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